JPH10338869A - Curable photochromic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable photochromic compsn. which exhibits a high coloration density and a high fading rate and is suitable for ophthalmic lenses by compounding a polymerizable tri- to hexafunctional (meth)acrylate monomer (e.g. trimethylolpropane trimethacrylate), optionally another acrylate monomer or a styryl monomer, and a photochromic compd. SOLUTION: This compsn. is prepd. by compounding 100 pts.wt. monomer component comprising 10-100 pts.wt. polymerizable tri- to hexafunctional (meth) acrylate monomer, such as of formula I (wherein Z<1> is an org. group of formula II; R<1> is II or 1-4C alkyl; a is 3 or 4; R<5> is H or CH3 ; R<6> is ethylene or propylene; d is 0-10; and e is 0 or 1), and 0-90 pts.wt. monomer selected from among polymerizable difunctional (meth)acrylate monomers, other polymerizable (meth)acrylate monomers, and polymerizable styryl monomers with 0.001-10 pts.wt. photochromic compd. Fulgide and a spirooxazine compd. are suitable as the photochromic compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition suitable for producing a photochromic cured product having high photochromic properties, high color density, high fading speed, and small initial coloring.

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has attracted attention in recent years. When a compound is irradiated with light containing ultraviolet rays such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is performed. It is a reversible action that returns to its original color when it is stopped and placed in a dark place. Compounds having this property are called photochromic compounds, and compounds having various structures have been synthesized conventionally, but these photochromic compounds do not have a sufficient color density at around room temperature.

In addition, fulgide-based photochromic compounds (hereinafter, simply referred to as fulgide compounds), spirooxazine-based photochromic compounds (hereinafter, simply referred to as spirooxazine compounds), and chromene-based photochromic compounds (hereinafter, simply referred to as spirooxazine compounds) are known as photochromic compounds having improved color density. , Abbreviations for chromene compounds) and the like (US Pat. No. 4,882,438, US Pat. No. 49,606).
78, USP5130058, USP5106998,
JP-A-2-28154, JP-A-3-11074,
WO94 / 22854, WO95 / 05371, USP
4913544, EP 0600669). Although these photochromic compounds show high color density near room temperature, they return to their original colors when ultraviolet rays are blocked (hereinafter, referred to as
(Called the fading speed) is slow and unsatisfactory. Further, a spirooxazine compound or a chromene compound having a high coloring density has a problem that coloring without irradiation with ultraviolet rays (hereinafter, referred to as initial coloring) is large.

On the other hand, it is known that the photochromic properties are affected by a polymerizable monomer serving as a matrix, a polymerization catalyst, and an additive, and a method for solving the above problems of the photochromic compound by improving the matrix has been proposed. Have been. For example, US Pat. No. 3,627,690 proposes a composition in which a fading rate is improved by adding a trace amount of a basic component or a weakly acidic component to a chromene compound. Also, Japanese Patent Application Laid-Open No. 8-28631
No. 7 and JP-A-2-302754 disclose a photochromic composition in which a metal salt of a carboxylic acid is added to a photochromic compound to improve the color density and the fading speed. Furthermore, EP-0227337 proposes a method for producing a photochromic article in which the amount of a polymerization catalyst is reduced by using a specific polymerizable monomer and the decomposition of a specific spirooxazine compound is suppressed. .

However, when the above-mentioned method is applied to a system of a polymerizable composition generally used for eyeglass lenses, for example, there is a problem that a sufficient effect cannot be obtained or other physical properties are deteriorated. It became clear.

It is also known that if the hardness of a cured product is reduced by adding a monomer that lowers the glass transition temperature of the cured product to the curable composition, the color density of the photochromic compound increases. However, there is a problem in using this method in terms of material strength in applications such as eyeglass lenses.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to develop a new technique which makes up for the above-mentioned drawbacks of the prior art, that is, to increase the color density of the photochromic property while increasing the fading speed. , Small initial coloring,
In addition, an object of the present invention is to propose a photochromic curable composition that satisfies the physical properties of the cured product.

[0008]

We have a high color density, a fast fade rate and a small initial coloration.
In order to obtain a photochromic cured product represented by a photochromic lens, intensive studies on various curable compositions have been continued. As a result, the present inventors have found that a photochromic curable composition containing a specific polymerizable monomer gives a photochromic cured product having not only a high color density of photochromic properties, a high fading speed, but also a small initial coloring. The invention has been completed.

That is, the present invention provides [1] (i) (A): a trifunctional to hexafunctional (meth) acrylate polymerizable monomer represented by the following general formula (1) or (3): 10-1
00 parts by weight and (ii) (B): the following general formula (4)
(C): a (meth) acrylate polymerizable monomer other than the above (A) and (B), or (D): styryl polymerization [2] The photochromic compound is used in an amount of 0.001 to 1 based on 100 parts by weight of the polymerizable monomer composed of 0 to 90 parts by weight of the polymerizable monomer composed of at least one of the reactive monomers.
It is a photochromic curable composition characterized by containing 0 parts by weight.

[0010]

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Wherein Z ¹ is the following general formula (2)

[0012]

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In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an ethylene group or a propylene group, and d is 0
It is an integer of 10 to 10 (when d is 0, it represents a mere bond), and e is 0 or 1 (when e is 0, it represents a mere bond). Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and a is 3 or 4. ]

[0014]

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[0015] {wherein an organic group represented by Z ² and Z ³ good Formula be different from one another (2), R ²
And R ⁴ are a hydrogen atom which may be different from each other or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and R ³ is an alkylene group having 1 to 4 carbon atoms or -CH ₂ O
CH ₂ —, b and c are each an integer of 0 to 3, and b + c is 3 to 6. ｝

[0016]

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(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group which may be different from each other;
And g are each an integer of 0 to 14, and f + g is 3 to
14. In the photochromic curable composition of the present invention, (A):
Trifunctional to 6 represented by the general formula (1) or (3)
By blending a functional (meth) acrylate polymerizable monomer, a cured product that can be suitably used for eyeglass lenses and the like having improved photochromic properties such as coloring density, fading speed, and initial coloring can be provided. .

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The photochromic curable composition of the present invention comprises (i) (A) a trifunctional to hexafunctional (meth) acrylate represented by the general formula (1) or (3). Polymerizable monomer (hereinafter, simply referred to as component (A))
10 to 100 parts by weight, and (ii) (B): a bifunctional (meth) acrylate-based polymerizable monomer represented by the following general formula (4) (hereinafter, also simply referred to as component (B)):
(C): (meth) acrylate-based polymerizable monomer other than the above (A) and (B) {hereinafter simply referred to as component (C)}, or (D): styryl-based polymerizable monomer} or less A polymerizable monomer consisting of 0 to 90 parts by weight of at least one polymerizable monomer consisting of at least one of the components (D) (hereinafter also simply referred to as the polymerizable monomer [1]). I do.

The component (A) in the polymerizable monomer [1] is not particularly limited as long as it is a (meth) acrylate polymerizable monomer represented by the general formula (1) or (3). Here, R ¹ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Here, the number of carbon atoms does not include the number of carbon atoms in the substituent (hereinafter, when referring to the number of carbon atoms in other groups, the number of carbon atoms in the substituent is not included). Specific examples of the alkyl group include:
Examples include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a t-butyl group. As the substituent which these alkyl groups may have, known substituents are used without any limitation. Specific examples of the substituent include a hydroxyl group, a halogen atom such as fluorine, chlorine, bromine and iodine, and an alkoxy group such as a methoxy group, an ethoxy group and a propoxy group. A in Formula (1) is 3 or 4. When a is 2 or less, it is impossible to achieve both improvement in photochromic properties and physical properties of the cured product.

Z ¹ in the general formula (1) is represented by the general formula (2). R ⁶ in the general formula (2) is an ethylene group or a propylene group. R ⁶ may be any of these groups, but is preferably an ethylene group from the viewpoint of increasing the hardness of the cured product, and is preferably a propylene group from the viewpoint of reducing initial coloring of photochromic properties. D is an integer of 0 to 10 (when d is 0, it represents a simple bond). When d exceeds 10, the hardness of the cured product becomes small, and the effect of the present invention is not sufficiently exhibited. The more preferable range of d is 0-6. E is 0 or 1 (when e is 0, it represents a simple bond). When e is 2 or more, it is not realistic because it becomes extremely difficult to obtain a raw material. Further, e is preferably 1 in consideration of the stability of the monomer.

In the general formula (3), Z ² and Z ³ each independently have the same meaning as Z ¹ in the general formula (1) and are represented by the general formula (2). Also. R ³ in the general formula (3) is an alkylene group having 1 to 4 carbon atoms or —CH ₂ OCH ₂
-. As the alkylene group, known groups can be used without any limitation. Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a dimethylmethylene group, and a 1,2-dimethylethylene group. And the like. R ³ may be either an alkylene group or —CH ₂ OCH ₂ —, but is preferably —CH ₂ OCH ₂ — from the viewpoint of easy availability of raw materials.

R ² and R ⁴ in the general formula (3) are a hydrogen atom which may be different from each other or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Here, as the alkyl group having 1 to 4 carbon atoms which may have a substituent, those similar to the aforementioned R ¹ can be mentioned.

In the general formula (3), b and c are each an integer of 0 to 3, and b + c is 3 to 6. b
When + c is less than 3, it is impossible to achieve both improvement in photochromic properties and physical properties of the cured product.

Specific examples of compounds which can be suitably used as component (A) in the present invention include: 1) trimethylolpropane trimethacrylate 2) 1,1,1-tris (methacryloyloxyethoxymethyl) propane 3) 1, 1,1-tris (methacryloyloxyethoxymethyl) -2-hydroxyethane 4) 1,1,1-tris (methacryloyloxyethoxymethyl) -2-methoxyethane 5) 1,1,1-tris (methacryloyloxyethoxymethyl) ) -2-Chloroethane 6) 1,1,1-tris [methacryloyloxytri (ethoxy) methyl] propane 7) 1,1,1,1 ′, 1 ′, 1′-hexa (methacryloyloxyethoxymethyl) ethyl ether 8) 1,1,1,3,3,3-hexa [methacryloyloxyno (Ethoxy) methyl] propane 9) 1,1,1-tris (acryloyloxy ethoxymethyl) can be mentioned propane.

The amount of the component (A) in 100 parts by weight of the polymerizable monomer [1] used in the photochromic curable composition of the present invention is 10 to 100 parts by weight, preferably 10 to 100 parts by weight.
90 parts by weight, more preferably 20 to 80 parts by weight. When the amount of the component (A) in 100 parts by weight of the polymerizable monomer [1] is 1
When the amount is less than 0 parts by weight, it is difficult to achieve both improvement of photochromic properties and physical properties of the cured product. The component (A) is an essential component for achieving both improvement of the photochromic properties and retention of the physical properties of the cured product, and its mechanism of action is not clear. It can be estimated that the free volume increases. Therefore, it is considered that the photochromic compound can move relatively freely in the matrix, the color density is increased, and the fading speed is increased.

The effect of the present invention is exhibited even when only the component (A) is used as the polymerizable monomer [1]. However, the moldability of the composition is improved and the physical properties and photochromic properties of the obtained cured product are improved. In order to improve the content, a polymerizable monomer comprising at least one of the component (B), the component (C) and the component (D) is added up to 90 parts by weight in 100 parts by weight of the polymerizable monomer [1]. It does not matter.

The component (B) in the polymerizable monomer [1] is not particularly limited as long as it is a (meth) acrylate polymerizable monomer represented by the general formula (4). Here, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (4) are hydrogen atoms or methyl groups which may be different from each other. R ⁸ and R ⁹
Is preferably a hydrogen atom from the viewpoint of increasing the hardness of the cured product, and is preferably a methyl group from the viewpoint of reducing initial coloring of photochromic properties.

In the general formula (4), f + g is 3 to
14. When f + g is larger than 14, the hardness of the cured product becomes small, and when f + g is smaller than 3, the cured product becomes brittle. The more preferable range of f + g is 4-9.

Specific examples of the compounds which can be suitably used as the component (B) in the present invention include: 1) triethylene glycol dimethacrylate 2) tetraethylene glycol dimethacrylate 3) nonaethylene glycol dimethacrylate 4) tetradecaethylene glycol Dimethacrylate 5) tripropylene glycol dimethacrylate 6) tetrapropylene glycol dimethacrylate 7) nonapropylene glycol dimethacrylate 8) nonaethylene glycol diacrylate.

The component (B) in the composition of the present invention is suitably used for adjusting physical properties of a cured product. That is, when the amount of the component (A) in the polymerizable monomer [1] is large, the cured product tends to be hard, and when the amount of the component (B) is large, the cured product tends to be soft. Therefore, the amount of the component (B) is appropriately determined in the range of 0 to 90 parts by weight based on 100 parts by weight of the polymerizable monomer [1] according to the hardness (or softness) required for each application. do it. The preferred amount of the component (B) is 0 to 70 parts by weight, more preferably 0 to 60 parts by weight, based on 100 parts by weight of the polymerizable monomer [1].

By blending the component (C) with the polymerizable monomer [1], the durability of the photochromic compound can be increased, and the refractive index of the cured product can be adjusted. The component (C) is not particularly limited as long as it is a (meth) acrylate polymerizable monomer other than the components (A) and (B). Examples of preferably used component (C) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxybutyl methacrylate, and 3- (glycidyl-2). −
(Oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3- (glycidyloxy-2-hydroxypropyloxy) -2
-Hydroxypropyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, tribromophenyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, alkoxy polypropylene glycol (meth) acrylate, trifluoromethyl (meth) Monofunctional (meth) acrylate monomers such as acrylate; polybutylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentene Glycol di (meth) acrylate, acrylic acid and methacrylic acid ester compounds of 2,2'-bis (4-methacryloyloxyethoxyphenyl) propane, and acrylic of 2,2'-bis (4-methacryloyloxy polyethoxyphenyl) propane Acid and methacrylic acid ester compounds, acrylic acid and methacrylic acid ester compounds of 2,2′-bis (4-methacryloyloxypropoxyphenyl) propane,
Acrylic acid and methacrylic acid ester compounds of 2,2'-bis (4-methacryloyloxy-polypropoxyphenyl) propane, acrylic acid of 2,2'-bis (3,5-dibromo-4-methacryloyloxyethoxy) propane and Methacrylic acid ester compounds, acrylic acid and methacrylic acid ester compounds of water-added bisphenol A ethylene oxide or propylene oxide adducts, dimethylol tricyclodecane di (meth) acrylate, dimethylol tricyclodecane polyethoxydi (meth) acrylate, trimethyl Methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, reaction product of ethylene glycol or polyethylene glycol with glycidyl (meth) acrylate, propylene Reaction product of glycidyl (meth) acrylate with glycol or polypropylene glycol, reaction product of bisphenol A ethylene oxide or propylene oxide adduct with glycidyl (meth) acrylate, water-added bisphenol A ethylene oxide or propylene oxide adduct with glycidyl (meth) ) Acrylate reaction products, polyfunctional (meth) acrylate monomers such as urethane acrylate, and the like. These (meth) acrylate monomers may be used alone or as a mixture of two or more, and the mixing ratio may be determined according to the intended use. The amount of the component (C) in 100 parts by weight of the polymerizable monomer [1] is from 0 to 90.
The amount is not particularly limited as long as it is within the range of parts by weight, but it is preferable to select so as to be 70 parts by weight or less, particularly 0.1 to 60 parts by weight.

The component (D) functions to enhance the moldability of the polymerizable monomer [1]. The component (D) is not particularly limited as long as it is a styryl polymerizable monomer. Suitable for use (D)
Examples of the component include styrene, chlorostyrene, α-methylstyrene, α-methylstyrene dimer, vinylnaphthalene, isopropenylnaphthalene, bromostyrene, divinylbenzene, and the like. These styryl monomers can be used alone or as a mixture of two or more kinds, and the compounding ratio may be determined according to the intended use. The amount of the component (D) in 100 parts by weight of the polymerizable monomer [1] is from 0 to 9
There is no particular limitation as long as it is within the range of 0 parts by weight, but it is preferable to select the amount so as to be 70 parts by weight or less, particularly 0.1 to 60 parts by weight.

Next, the photochromic compound used in the present invention will be described. As the photochromic compound used in the present invention, a compound exhibiting a photochromic action can be employed without any limitation. For example, photochromic compounds such as fulgide compounds, chromene compounds and spirooxazine compounds are well known, and these photochromic compounds can be used in the present invention. Examples of the above photochromic compound include USP 4,882,438 and USP 4,960.
678, USP 5130058, USP 510699
8, WO94 / 22854, WO95 / 05371, U
Compounds known from SP4913544, EP06060069 and the like can be suitably used. These photochromic compounds can be used alone or as a mixture of two or more, and the compounding ratio may be determined according to the intended use.

Of the above photochromic compounds, chromene compounds and spirooxazine compounds can be suitably used because the effect of improving the photochromic properties according to the present invention is particularly large as compared with other photochromic compounds. A chromene compound that can be suitably used in the present invention can be represented by the general formula (5).

[0035]

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Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are
A hydrogen atom, an alkyl group, an aryl group, a substituted amino group, a saturated heterocyclic group or an unsaturated heterocyclic group, which may be the same or different, and R ¹³ and R ¹⁴ may form a ring together;

[0037]

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The group represented by is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may have a substituent. In the formula (5), examples of the alkyl group represented by R ¹¹ , R ¹² , R ^13, and R ¹⁴ include an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, and an aryl group Examples thereof include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the substituted amino group include an amino group in which at least one hydrogen atom has been substituted with the above-described alkyl group or aryl group, and a saturated heterocyclic group includes a pyrrolidine ring, an imidazolidine ring, and a piperidine. ring,
Nitrogen atom, oxygen atom such as piperazine ring, morpholine ring,
Or containing 1 to 2 sulfur atoms as ring constituent atoms
A monovalent group derived from a 6-membered ring can be exemplified.
Examples of the unsaturated heterocyclic group include groups having 4 to 9 carbon atoms derived from a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an indole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, and the like. Can be mentioned.

In the above formula (5), the ring formed by R ¹³ and R ¹⁴ together includes a norbornylidene group, a bicyclo [3.3.1] 9-nonylidene group and the like.

In the above equation (5),

[0041]

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Among the divalent groups represented by the above, the divalent aromatic hydrocarbon group includes one benzene ring or two to three
And a divalent group derived from two condensed rings, and examples of the divalent unsaturated heterocyclic group include an oxygen atom,
A nitrogen atom or a sulfur atom as a ring-constituting atom;
And a divalent group derived from a 5- to 7-membered ring or a condensed ring thereof with a benzene ring. Specific examples of the divalent aromatic hydrocarbon group include a group having 6 to 14 carbon atoms derived from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, and the like. Specific examples of the saturated heterocyclic group include a furan ring, a benzofuran ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrrole ring, a thiophene ring, a thiophene ring, and a benzothiophene ring.
And the group of

These substituents are not particularly restricted but include, for example, halogen atoms such as chlorine, bromine and iodine:
An alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group:
C1-C10 alkoxy groups such as methoxy and ethoxy groups: C6 carbon atoms such as phenyl, tolyl, and xylyl groups
Aryl groups having 10 to 10: alkoxyaryl groups having 7 to 14 carbon atoms (aryl groups having 6 to 10 carbon atoms substituted by alkoxy groups having 1 to 4 carbon atoms): piperidino group, morpholino group, indolino group, dimethylamino group C1-C1 such as
0 substituted amino group: nitro group: cyano group and the like.

As the chromene compound represented by the general formula (5), particularly, R ¹¹ and R ¹² are both hydrogen atoms, R ¹³ and R ¹⁴ are the same or different aryl groups, or an unsaturated heterocyclic compound. A bicyclo which is a cyclic group or is formed together with these [3.3.
1] a 9-nonylidene group or a norbornylidene group,

[0045]

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Is a compound derived from a naphthalene ring which may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a substituted amino group having 1 to 10 carbon atoms. It can be suitably used.

The spirooxazine compound suitably used in the present invention can be represented by the following general formula (6).

[0048]

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Here, in the general formula (6), R ¹⁵ and R
¹⁶ and R ¹⁷ are the same or different alkyl groups, cycloalkyl groups, cycloalkyl groups, alkoxy groups, alkyleneoxyalkyl groups, alkoxycarbonyl groups, alkoxycarbonylalkyl groups, aryl groups, aralkyl groups, aryloxy groups, alkylenethio groups; An alkyl group, an acyl group, an acyloxy group or an amino group, R ¹⁶ and R ¹⁷ may together form a ring, and R ¹⁵ , R ¹⁶ and R ¹⁷ may have a substituent; As the substituent, in addition to the groups described above, a halogen atom,
Examples include a nitro group, a cyano group or a heterocyclic group. Also,

[0050]

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The group represented by is an optionally substituted aromatic hydrocarbon group or an unsaturated heterocyclic group,

[0052]

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The group represented by is an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group.
As the substituent, the same groups as those described above for R ¹⁵ , R ¹⁶ and R ¹⁷ can be selected.

[0054]

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(Provided that R ¹⁸ and R ¹⁹ are an optionally substituted alkyl group, alkoxy group or allyl group, and R ¹⁸ and R ¹⁹ are bonded to each other and cyclized to form a nitrogen-containing heterocyclic ring. The group represented by the formula (1) is preferable in that the color density is high in the initial photochromic performance.

The effect of improving the photochromic properties in the present invention is also exerted on fulgide compounds. The fulgide compound used in the present invention is represented by the general formula (7).

[0057]

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[However,

[0059]

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Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group, and R ²⁰ is an alkyl group, an aryl group or a monovalent heterocyclic group. And

[0061]

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Is a norbornylidene group or an adamantylidene group, and X is an oxygen atom, a group> NR ²¹ , a group> NA ₁ -B _1- (A ₂ ) _m- (B ₂ ) _n- R ²² , a group> NA ₃ -A ₄ , or a group> NA ₃ -R ²³ , wherein R ²¹ is a hydrogen atom, an alkyl group or an aryl group, and A ₁ , A ₂ And A ₃ may be the same or different, an alkylene group, an alkylidene group,
A cycloalkylene group or an alkylcycloalkane-diyl group, wherein B ₁ and B ₂ may be the same or different,

[0063]

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Wherein m and n each independently represent 0 or 1, when m is 0, n is 0, and R ²² is an alkyl group, a naphthyl group or a naphthyl group. A ₄ is an alkyl group, A ₄ is a naphthyl group,
²³ is a halogen atom, a cyano group or a nitro group. )] In the above formula (7),

[0065]

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The aromatic hydrocarbon group or unsaturated heterocyclic group represented by the formula (5) is the same as the group in the formula (5), and the substituent of each group is not particularly limited. Halogen atom such as iodine: alkyl group having 1 to 20 carbon atoms such as methyl group and ethyl group: alkoxy group having 1 to 20 carbon atoms such as methoxy group and ethoxy group: carbon number such as phenyl group, tolyl group and xylyl group 6 to 10 aryl groups: amino groups: nitro groups: cyano groups and the like.

In the above formula (7), the alkyl group, aryl group and heterocyclic group represented by R ^{20 have the} above-mentioned C 1 -C 1
From an alkyl group of 4, an aryl group having 6 to 10 carbon atoms, and a 5- to 7-membered ring containing 1 to 2 oxygen, nitrogen, or sulfur atoms as ring constituent atoms or a condensed ring thereof with a benzene ring Derived monovalent groups can be mentioned.

In the above formula (7), the alkyl group and the aryl group represented by R ²¹ are the same as those of the above R ²⁰ . The alkylene group represented by A ₁ , A ₂ and A ₃ is preferably a group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and the alkylidene group is ethylidene. Group, a propylidene group, an isopropylidene group or the like having 2 to 4 carbon atoms, and a cycloalkylene group is preferably a cyclohexylene group, and an alkylcycloalkane-diyl group is a dimethylcyclohexane-diyl group. Is preferred.

In the above formula (7), the alkyl group represented by R ²² is the same as the above R ²⁰ , and the naphthylalkyl group is a group having 1 carbon atom such as a naphthylmethyl group and a naphthylethyl group.
It is preferably a group of 1 to 14.

Among the fulgide compounds represented by the above formulas, considering the durability of the photochromic action and the like, R
²⁰ is an alkyl group, X is> NR, and R is a cyanoalkyl group having 1 to 4 carbon atoms, a nitroalkyl group having 1 to 4 carbon atoms, or an alkoxycarbonylalkyl group having 3 to 9 carbon atoms ( C1-C4 alkoxy group and C1-C1
4 comprising an alkylene group),

[0071]

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Is an adamantylidene group,

[0073]

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Is an aryl group having 6 to 10 carbon atoms or an alkoxyaryl group having 7 to 14 carbon atoms (1 to 4 carbon atoms).
The compound is preferably a heterocyclic group which may be substituted with an aryl group having 6 to 10 carbon atoms and substituted with an alkoxy group, particularly a group derived from a thiophene ring.

When the curable composition of the present invention is used for an eyeglass lens, a color tone such as gray or brown is preferred. However, such a color tone cannot be obtained by a single photochromic compound. Of different photochromic compounds are used. The above-mentioned fulgide compound and spirooxazine compound generally develop an orange-blue color, but by mixing a chromene compound which develops a yellow-orange color, an intermediate color such as gray or brown can be obtained.

Specific examples of the chromene compound, spirooxazine compound and fulgide compound which can be suitably used as the photochromic compound in the present invention include the following compounds.

Chromene compound: 1) Spiro [norbornane-2,2 '-[2H] benzo [h] chromene] 2) Spiro [bicyclo [3.3.1] nonane-9,2'
-[2H] benzo [h] chromene] 3) 7'-methoxyspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [h] chromene] 4) 7'-methoxyspiro [ Norbornane-2,2'-
[2H] benzo [h] chromene] 5) 3,3-bis (3-fluoro-4-methoxyphenyl) -6-morpholino-3H-benzo [f] chromene 6) 3,3-bis (4-methoxyphenyl) ) -6-morpholino-3H-benzo [f] chromene 7) 3- (3-trifluoromethyl-4-methoxyphenyl) -3- (4-methoxyphenyl) -6-thiomorpholino-3H-benzo [f] Chromene spirooxazine compound: 1) 1′-methoxycarbonylmethyl-8 ″ -methoxy-6 ″-(4-methylpiperazino) dispiro (cyclohexane-1,3 ′-(3H) indole-2 ′-(1 ′)
H), 3 ''-(3H) naphtho (3,2-a) (1,4)
Oxazine) 2) 6'-fluoro-1 ', 5'-dimethyl-6''-morpholinodispiro(cyclohexane-1,3'-(3
H) Indole-2 '-(1'H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine) 3) 6'-Fluoro-5'-methyl-1'- Isobutyl-6 ″ -morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(1'H), 3 ''-
(3H) naphtho (3,2-a) (1,4) oxazine) 4) 3 ′, 3′-dimethyl-1′-isopropyl-6 ″
-Indolinospiro- (3H) indole-2'-
(1′H), 3 ″-(3H) naphtho (3,2-a)
(1,4) oxazine 5) 3 ′, 3′-dimethyl-1′-isobutylspiro-
(3H) indole-2 '-(1'H), 3''-(3
H) Naphtho (3,2-a) (1,4) oxazine fulgide compound: 1) N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophene Carboximide-7,2-tricyclo [3.3.
1.1] Decane) 2) N-cyanomethyl-6,7-dihydro-2- (p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 3) N-cyanomethyl-6,7-dihydro-4 -Methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 4) 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl- 2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 5) 6,7-dihydro-4-methyl-2- (p -Methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 6) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-3-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 7) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-spiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.
1] Decane) The compounding amount of the photochromic compound in the photochromic curable composition of the present invention depends on the amount of the polymerizable monomer [1] 10
It is in the range of 0.001 to 10 parts by weight with respect to 0 parts by weight. If the amount of the photochromic compound is less than 0.001 part by weight per 100 parts by weight of the polymerizable monomer [1], the reversible durability of the photochromic property is impaired,
When the amount exceeds 10 parts by weight, the initial coloring of the cured product becomes large. A suitable amount of the photochromic compound for obtaining good photochromic performance is 0.01 to 5 parts by weight, particularly 0.01 to 1 part by weight, per 100 parts by weight of the polymerizable monomer [1]. is there.

The photochromic curable composition of the present invention further comprises a releasing agent, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, a dye, a pigment, Various stabilizers and additives such as fragrances can be mixed and used as needed.

It is preferable to use a mixture of the above-mentioned ultraviolet stabilizers because the durability of the photochromic compound can be further improved. In particular, since the fulgide compound has a large effect of improving the durability by the ultraviolet light stabilizer, when the fulgide compound and the chromene compound are mixed and used as described above, the change in the intermediate color of these compounds with time is good. Can be prevented.

As the ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol light stabilizer, and a sulfur-based antioxidant can be suitably used.

The amount of the UV stabilizer used is not particularly limited, but is usually 0.001 to 10 based on 100 parts by weight of the polymerizable monomer [1].
It is preferable that the amount be in the range of 0.01 to 1 part by weight.

Further, when a fulgide compound and a chromene compound are used in combination, by adding a phosphite compound, it is possible to suppress the change over time of the mixed color of these photochromic compounds. Therefore, it is most preferred in the present invention to use both the above-mentioned ultraviolet stabilizer and phosphite compound in a system in which a fulgide compound and a chromene compound are used in combination. The compounding amount of the phosphite compound is 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, per 100 parts by weight of the polymerizable monomer [1].
It is preferably 1 part by weight.

Further, when an infrared absorbing agent is mixed and used, a photochromic cured product having an infrared absorbing ability in addition to the photochromic action can be obtained. As the infrared absorber, polymethine compounds, diimonium compounds, cyanine compounds, anthraquinone compounds, and aluminum compounds can be used, but diimonium compounds having a large molecular extinction coefficient and exhibiting an effect when added in a small amount are preferable. is there.

The compounding amount of the infrared absorber is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.01 part by weight, per 100 parts by weight of the polymerizable monomer [1].

The polymerization method for obtaining a cured product from the photochromic composition of the present invention is not particularly limited, and a known radical polymerization method can be employed. The polymerization can be initiated by using a radical polymerization initiator such as various peroxides or azo compounds, or by irradiating ultraviolet rays, α rays, β rays, γ rays, or a combination of both. As a typical polymerization method, for example, a photochromic composition of the present invention mixed with a radical polymerization initiator is injected between a mold held by an elastomer gasket or a spacer, oxidized in an air furnace, and then removed. Mold polymerization is employed.

The radical polymerization initiator is not particularly limited, and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and the like. Diacyl peroxides such as acetyl peroxide; peroxyesters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate and t-butylperoxybenzoate; diisopropyl Percarbonates such as peroxydicarbonate and di-sec-butylperoxydicarbonate; azo compounds such as azobisisobutyronitrile;

The amount of the radical polymerization initiator used depends on the polymerization conditions, the type of the initiator and the composition of the above-mentioned monomer.
Although it cannot be limited unconditionally, generally, 0.001 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer [1],
Preferably, the range is 0.01 to 5 parts by weight.

Among the polymerization conditions, particularly the temperature affects the properties of the obtained photochromic cured product. The temperature condition is affected by the type and amount of the initiator and the type of the monomer, and thus cannot be unconditionally limited. Generally, the polymerization is started at a relatively low temperature, and the temperature is gradually increased. It is preferable to perform a so-called tapered two-stage polymerization in which the composition is cured at a high temperature at the time of completion. Since the polymerization time also varies depending on various factors like the temperature, it is preferable to determine an optimum time in advance according to these conditions, but in general, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

Further, the photochromic cured product obtained by the above method can be subjected to the following treatment depending on the use. That is, dyeing using a dye such as a disperse dye, a silane coupling agent and silicon, zirconium,
Antimony, aluminum, tin, or a hard coat agent composed mainly of sol such as tungsten, SiO _2, Ti
Processing such as antireflection treatment and antistatic treatment by vapor deposition of a thin film of a metal oxide such as O ₂ or ZrO ₂ or application of a thin film of an organic polymer, and secondary treatment can also be performed.

[0090]

The cured product obtained by polymerizing the photochromic curable composition of the present invention is excellent not only in the color development density of photochromic properties, the fading speed and the initial coloring, but also
Excellent in physical properties such as hardness of the cured product. Further, a photochromic cured product excellent in transparency, solvent resistance, heat resistance, impact resistance, coatability, and dyeability can be obtained.

Therefore, the cured product obtained by polymerizing the photochromic composition of the present invention is useful as an organic glass having photochromic properties, and can be suitably used, for example, for applications such as photochromic lenses.

[0092]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

The components (A) to (D) and the photochromic compound used in the following examples are the following compounds.

Component (A) trifunctional to hexafunctional (meth) acrylate monomer: TMPT: trimethylolpropane trimethacrylate TMEP: 1,1,1-tris (methacryloyloxyethoxymethyl) propane TEOE: 1,1 1,1-tris (methacryloyloxyethoxymethyl) -2-hydroxyethane TECE: 1,1,1-tris (methacryloyloxyethoxymethyl) -2-chloroethane TMTP: 1,1,1-tris [methacryloyloxytri (ethoxy) Methyl] propane HMEE: 1,1,1,1 ', 1', 1'-hexa (methacryloyloxyethoxymethyl) ethyl ether Bifunctional (meth) acrylate monomer of component (B): 3PG: tripropylene glycol Dimethacrylate 4PG: Tetrapropyl Glycol dimethacrylate (a mixture of polypropylene glycol dimethacrylate and a monomer having an average number of oxypropylene chains of 4) 9PG: Nonapropylene glycol dimethacrylate (a mixture of polypropylene glycol dimethacrylate and an average number of moles of oxypropylene chains 4G: tetraethylene glycol dimethacrylate (a mixture of polyethylene glycol dimethacrylate having an average number of moles of oxyethylene chain of 4) (G) a (meth) acrylate-based monomer of component (C) GMA: glycidyl methacrylate HEMA: 2-hydroxyethyl methacrylate BPE: 2,2-bis (methacryloyloxyethoxyphenyl) propane (D) Component styryl monomer MS: α-methylstyrene D MS: α-methylstyrene dimer photochromic compound: chromene compound; c1: spiro [bicyclo [3.3.1] nonane-9,
2 '-[2H] benzo [h] chromene c2: 7'-methoxyspiro [bicyclo [3.3.1]
Nonane-9,2 '-[2H] benzo [h] chromene c3: 3,3-bis (3-fluoro-4-methoxyphenyl) -6-morpholino- [3H] benzo [f] chromene c4: 3 3-bis (4-methoxyphenyl) -6-morpholino- [3H] benzo [f] chromene spirooxazine compound; s1: 6′-fluoro-1 ′, 5′-dimethyl-6 ″-
Morpholinodispiro (cyclohexane-1,3 ′-(3
H) Indole-2 '-(1'H), 3''-(3H) naphtho (3,2-a) (1,4) oxazine) s2: 6'-fluoro-5'-methyl-1'- Isobutyl-6 ″ -morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(1'H), 3 ''-
(3H) naphtho (3,2-a) (1,4) oxazine) s3: 3 ′, 3′-dimethyl-1′-isobutylspiro- (3H) indole-2 ′-(1′H), 3 ′ '-(3
H) Naphtho (3,2-a) (1,4) oxazine fulgide compound; f1: N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophene Carboximido-7,2-tricyclo [3.
3.1.1] decane) f2: N-cyanomethyl-6,7-dihydro-2- (p
-Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) f3: N-cyanomethyl-6,7-dihydro- 4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) Examples 1 to 17 and Comparative Examples 1 to 3 The composition comprising the components A) to (D) and the photochromic compound was added with t
1 part by weight of -butylperoxy-2-ethylhexanate was added and mixed well. This mixture was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out using an air furnace at 30 ° C. to 90 ° C. for 18 hours, and the temperature was gradually increased and kept at 90 ° C. for 2 hours. After the polymerization was completed, the mold was removed from the air oven, and after cooling, the cured product was removed from the glass mold of the mold.

[0095]

[Table 1]

[0096]

[Table 2]

The photochromic properties of the obtained photochromic cured product and physical properties of the cured product were tested by the following methods.

(1) Coloring Tone and Coloring Density The obtained photochromic cured product (2 mm in thickness) was coated with a xenon lamp L-2480 (300 mm, manufactured by Hamamatsu Photonics).
W) SHL-100 was passed through an aeromass filter (manufactured by Corning Incorporated) at 20 ° C. ± 1 ° C. at a beam intensity of 365 nm = 2.4 mW / cm ² at the photochromic cured body surface.
Irradiation was performed at 245 nm = 24 μW / cm ² for 120 seconds to form a color, and the color tone was visually determined. Also, ε (120
Second) −ε (0 second) was obtained and defined as the color density. However,
ε (120 seconds) is the absorbance of the photochromic cured body at the maximum absorption wavelength after the light irradiation for 120 seconds under the above conditions, and ε (0 seconds) is the unirradiated cured body at the maximum absorption wavelength during light irradiation. Is the absorbance of

(2) Fading speed The time required for the color density obtained in (1) to decrease to _1/2 was represented by t _1/2 .

(3) Initial Coloring In the state without irradiation with a xenon lamp, the initial coloring was represented by the absorbance at the maximum absorption wavelength.

(4) Surface Hardness Using a Rockwell hardness tester, the value of the cured product having a thickness of 2 mm on an L-scale was measured.

Table 2 shows the results of evaluating the physical properties of each cured product.

[0103]

[Table 3]

[0104]

[Table 4]

Claims (2)

[Claims] [1] (1) (i) (A): the following general formula (1)
Or 10 to 100 parts by weight of a trifunctional to hexafunctional (meth) acrylate polymerizable monomer represented by the general formula (3),
And (ii) (B): 2 represented by the following general formula (4)
Functional (meth) acrylate polymerizable monomer, (C):
(Meth) acrylate-based polymerizable monomer other than (A) and (B) or (D): 0 to 90 parts by weight of a polymerizable monomer comprising at least one of styryl-based polymerizable monomers [2] with respect to 100 parts by weight of the polymerizable monomer comprising
A photochromic curable composition comprising 0.001 to 10 parts by weight of a photochromic compound. Embedded image [Wherein, Z ¹ is the following general formula (2): In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an ethylene group or a propylene group, d is an integer of 0 to 10 (when d is 0, it represents a simple bond), e is 0 or 1 (when e is 0, it represents a mere bond). ｝
Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent;
Is 3 or 4. [Chemical formula 3] 中 In the formula, Z ² and Z ³ are organic groups represented by the general formula (2) which may be different from each other, and R ² and R ⁴ have a hydrogen atom or a substituent which may be different from each other Is an alkyl group having 1 to 4 carbon atoms, and R ³ is an alkylene group having 1 to 4 carbon atoms or —CH ₂ OCH ₂ —,
b and c are each an integer of 0 to 3, and b + c is 3 to
6. ｝ (Wherein, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group which may be different, f and g are each an integer of 0 to 14, and f + g is 3 to 14) .) 2. A photochromic cured product obtained by curing the photochromic curable composition according to claim 1.